Novel polymeric thiadiazinethiones



United States Patent 3,126,378 NOVEL POLYMERIC THIADIAZINETHIONES Earl W. Cummins, Wilmington, Del., assignoito E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed May 2, 1960, Ser. No. 25,856 1 Claim. (Cl. 260-243) are represented by the are same or difierent from group consisting of alkylene of 2-6 carbon atoms; R is hydrogen and alkyl or alkenyl (C -C and n is a positive whole number.

The stable polymeric thiadiazinethiones and compositions of this invention are efiective agents for the protection of organic matter subject to fungus infection as for example prevention of apple scab and tomato blight. Generally, the crude reaction products contain substantial amounts of the polymeric thiadiazinethiones of this invention and are adequate for direct formulation and use as fungicide agents without further purification.

A convenient method for the preparation of the novel polymeric thiadi-azi-nethiones follows: Generally the method involves the addition of an aqueous or aqueous-alcoholic solution of an alkylene diamine or a mixture of alkyl amines and alkylene diamines to an aqueousalcoholic solution of an alkylenebisdithiocarbamic acid or a mixture of mono and bisdithiocarbamic acids, followed by the immediate addition of an aqueous aldehyde solution.

3,126,378 Patented Mar. 24, 1964 The reaction is generally completed in about 1 to 2 hours under normal atmospheric conditions. The solid reaction mixtures containing substantial quantities of the polymeric thiadiazinethiones of this invention are then removed by filtration, washed with water and dried.

The degree of polymerization can be controlled by varying the ratio of the difunctional reactants (alkylene diamine, alkylenebisdithiocar-bamic acids and aldehyde) to the monofunctional reactants (alkyldithiocar-bamic acid and/ or alkyl amine). The type of polymer obtained is defined by the monofunctional reactants (i.e., the chain terminating reactants) used.

The chain terminating reactants are generally mixed with the alkylene diamine and the alkylenebisdithiocarbamic acid before the addition of the aldehyde. However, in some instances, the addition of the chain terminating reactants may be made simultaneously with the aldehyde throughout the course of the reaction. Unstable long-chain polymeric solids result unless the chain terminating reactants are added at least partially to the chain promoting reactants at the beginning of the reaction; prior to solid precipitation from the reaction medium.

The following subgeneric structures for the thiadiazinethiones of this invention illustrate generally that the polymerization can proceed and can be terminated or capped at both ends in three Ways by the appropriate use of the monofunctional and difunctional reactants mentioned above. v

(a) Alkyl amine moiety at both ends.

(b) N-alkyl dithiocarbamic acid moiety at both ends.

(c) Combination of a and b above.

('11) 1 ALKYL N AT BOTH ENDS ALKYLDITHIOCARBAMYL MOIETY 3 (IV) CAPPED \VITH ALKYL AMINE AND ALKYL DITHIOCARBAMYL MOIETIES S S II II C /G\ S N-R1N S These structure further illustrate that the thiadiazinethiones of this invention are linked by alkylene groups via their amino and thio amido nitrogens. The ratio of amino alkylene groups to thio amido alkylene groups in a given polymeric product is controlled by the molar ratios of the difunctional reactants used in the reaction. For example, the three types of polymeric thiadiazinethiones of this invention illustrated by Formulae II, 111, IV above are prepared by reacting the ratios of molar equivalents of Note that n of Formulae II, III, and IV above which defines the extent of polymerization and the n times the molar equivalents of the reactants listed in Table I are interrelated and numerically the same. For example when n=3 in Table I, the corresponding polymeric thiadiazinethione 11, HI, or IV containing 3 repeating units (n=3) are formed in substantial quantities.

The conditions of the reactions, for example, the exact temperature employed, the amount and type of solvent for the reactants, the rate of addition of the aldehyde, the concentration of the reactant solutions etc., will be dependent on the reactants employed and the extent of polymerization desired.

The fungicidal polymeric thiodiazinethiones of this invention are in general white solids having melting points in the range of 60200 C. They are essentially insoluble in water and alcohols.

In practicing the fungicidal methods of my invention, one or more of the active ingredients is applied to the organic material to be treated for the control of fungi at a dosage sutficient to exert fungicidal action. Accordingly, my compositions and methods are applicable for the protection of carbohydrates, proteins and fats. They are particularly suited for the treating of living plant life such as vegetables, ornamental plants and fruit-bearing trees. Also they can be used to treat organic fibers and fabrics, leather and various cellulosic materials such 4 as wood. Likewise they can be used to treat paints and lubricating oils.

In application to plants, fungicidal control is obtained in most instances by applying the active compound at a dosage or rate from about 1 to 10 pounds per acre, the optimum amount within this range being largely dependent upon the variables mentioned hereafter. It is, of course, determined by and dependent upon the particular fungicidal compound selected, the method of application, and, in the case of application to vegetation, the state and condition of growth of the vegetation to be treated, and the climatic conditions.

The fungicidal compositions of my invention contain in sufiicient amount to exert fungicidal action one or more of the above-described active compounds in admixture with a carrier material or conditioning agent of the kind used and commonly referred to in the art as a fungicide adjuvant or modifier. The conventional fungicide adjuvants are inert solids, hydrocarbon liquid diluents and surface-active agents. They provide formulations adapted for ready and efficient application using conventional applicator equipment. Usually from about 1 to 95% by weight of the fungicidal composition is active ingredient.

Solid compositions are preferably in the form of powders. They are compounded to be homogeneous powders that can be either used as such, diluted with inert solids to form dusts, or suspended in a suitable liquid medium for spray application. The powders usually comprise active ingredient admixed with minor amounts of conditioning agent. Natural clays, either adsorptive such as attapulgite or relative non-adsorptive such as kaolin clays, diatomaceous eanth, walnut shell flour, tobacco dust, redwood flour, synthetic fine silica, calcium silicate and other inert solid carriers of the kind conventionally employed in powder fungicidal compositions can be used. The active ingredient usually makes up from about 25 to of these powder compositions. For conversion of the powders to dusts, talc, pyrophyllite, tobacco dust, voloanic ash and other dense, rapid-settling inerts solids custcrnarily are used.

Liquid compositions employing one or more of the fungicidally-active ingredients are prepared by admixing the active ingredient with a suitable liquid diluent medium. The active ingredient can be either in solution or in suspension in the liquid medium. Typical of the liquid media commonly employed as fungicide adjuvants are kerosene, Stoddard solvent, xylene, alcohols, alkylated naphthalene and glycols. The active ingredient usually makes up from about 0.5 to 50% of these liquid compositions. Some of these compositions are designed to be used as such, and others to be extended with large quantities of water.

Compositions in the form of wettable powders or liquids in many cases also include one or more surfaceactive agents such as wetting, dispersing or emulsifying agents. These materials cause the composition to disperse or emulsify easily in water to give aqueous sprays.

The surface-active agents employed can be of the anionic, cationic or nonionic type. They include, for example, sodium oleate, sulfonated petroleum oils, alkyl aryl sulfonates, sodium lauryl sulfate, polyethylene oxides, ligm'n sulfonates, and other surfaceractive agents. A detailed list of such agents is set forth in an article by Mc- Cutcheon entitled ynthetic Detergents and Emulsifiers, volume 31, 1955, of Soap and Chemical Specialities.

In some cases it may be desirable to employ the active compounds of the present invention in combination with other fungicides to give compositions that have broad spectrum fungicidal activity. In these mixtures, the fungicidally active materials can be present in any desired amount, ordinarily from about 0.1-20 parts by weight of a compound represented by Formula 1 per part by weight of the auxiliary fungicidally active material. In some instances it may even be desirable to employ two or more auxiliary fungicides.

, 6 essentially quantitative yield of the stable, solid 5,5- (tetrahydro-2-thiono-2H- 1,3,5 -thiadiazin-3,5 -ylene) diethylene]bis(tetrahydro 3-methyl-2H-l,3,5-thiadriazine2- thione) is isolated by filtration. After washing with Water and drying, it is adequate for formulation and fungicidal application without further purification.

Other polymeric thiadiazirrethiones of this invention having the subgeneric structure -IV shown above can be prepared similarly by substituting equivalent molar quantitles of the reactants listed in Table 11 below for the reactants of Example 1 above. Multiples of the equivalent molar quantities of the difunotional reactants gives polymeric thiadiazinethiones of structure .1V where n f is greater than 1. For the purpose of clarity structural description of the products obtained are listed in Table II below rather th-an the language used to name the product obtained in Example 1 above.

Table I I Reaotants Products Obtained of Subgeneric Structure IV where R, R1, R2, R are- Alky1(Na Alkylenebis- EX. di-HCl salt H01 salt of Aldehyde dithiocardithiocar- Alkyl R R1 R: R3 11 N0. of diamlne amine bamic acid bamic acid 2Na salt 2 ethylene methylformaldeethyl..- ethylene. methyl.-- H ethylene. ethyleneethyl 1 diamine. amine. hyde. 3 do isoprpyl-- .-..do lsopropyL. doisopropyl isopropyl 1 4 do methyl h l d exyl 1 5 do do do.-.. lauryl 1 6 do ethylamlne ethyl.-- methy 1 7 do n-butylisobutyl.-. n-butyl rsobutyl..- 1

amine. allylamine do allyl allyl H allyl 1 amyl acfitadeoctadecylamyl ootadecyl- 1 y e. tert. oetyl... do methyl-. tert. octyl. moths 1.... 1 allyl propion- -.do.-.. allyl d 1 aldehyde. methyl..-. butyral- -..do methyl-.. methyl... 1

dehyde 13 trimethdo iormalde- ...do--.. ..-..do.-.. H do propylene-.. do. 1

ylene. hyde. V 14. ethylenen-propyl. acrolein. tert. octyl. hexemethn-propyl. vmyl hexinnethethylene. tert. oetyl. 1

y ene.- y ene. l5- hexamethmethyl-..- orotoniq. methyl.-- do methyl.-- methyl do hexamethmethyl... 1

ylene. viny ylene. 16- tetramethlauryl tormaldeheptyl. pentamethlauryl- H pentamethtetramethheptyl- 1 ylene. hyde. ylene. ylene. ylene. 17 ethylene methyl do methyl.-- ethylene. methyl...- do ethylene. ethylene. methyl--. 2 18 do do do o d (lo. d0 do .do.... 3 19 do do aorolein do.... vinyl d0 do do 4 20 trimethtert. butyl-. butyraln-butyltert. butyl propyl. trimethtnmethn-butyl 7 ylene. hyde. ylene. ylene. ylene. 21 ethylene. methyl forilmgldemethyl--. ethylene. methyL- H ethylene. ethylene. methyl-.- 10

Manganese dimethyl dithiocarbanrate plus Z-mercap-tobenzothiazole Copper dihydrazinium sulfate Copper-8-quinolinolate Cycloheximide Terramycin Streptomycin Compounds disclosed in: my copendin-g application Serial No. 809,597 filed April 29, 1959, now abandoned.

In order that the invention may be better understood, the following examples are given:

V PREPARATIVE EXAMPLES 7 Example 1.-A solution containing 1500- pts. by wt. of water, 256- pts. by wt. of ethylenebisditliio'carbamic' acid, disodium salt and 129 pts.

by wt. of methyl dithio- ,'give 527 .pts. by of 3,3'-ethylenebis[(tetrahydro-Z- carbamic acid, sodium salt is added rapidly at room temperature to a stirring solution containing 1000 pts. by:

wt. of water, drochloride and 67.5 pts. by wt. of niethylamine hydro 133 pts. by wt. of .ethylenediaminedihyreactants of Example 22 above.

chloride followed immediately by the rapidaddition of 600 pts. by wt. of a 30% aqueous solution of formalde=" hyde.

The entire reaction is stirred for two hours. An

thiono 2H 1,3,5 thiadiazin-3,5-ylene)diethylene1bis- (tet-rahydro-S-methyl-ZH-1,3,5-thiadiazine-2-thione) as a pale yellow solid, M.P. 156 164 C.

Otherpolyme-ric thiadiazinethiones of this invention having the subgeneric structure 11 shown above can be prepared similarly by substituting equivalent molar quantities of the reactants listed in Tablelll below for the Multiples of the'equivalent quantities of the difunctional reactants as shown in 'Table I gives the polymeric thiadiazinethiones of structure II where n is greater than one. For the purposes of clarity and understanding, structural identification of the products obtained are listed in Table III below:

The following examples further illustrate the fungicidal activity of the polymeric products of this invention:

Table III Reaetants Products Obtained f Subgcnerie Structure II where R, R1, R1, R3, aredi-HCl salt HCl salt of Alkylenebisdi- Ex. No. of diarnlne the amine Aldehyde thioearbamic R R1 R; R: n

acid, 2Na+ salt formaldehyde. ethylene 1 ,do do 1 aeetaldchyde .do- 1 propionoldo 1 dehyde. 27 trimethylene isopropyl butyral- --d0 propyl d0 tnmethlsopropyl 1 dehyde. ylene. 28 hexamethlauryl erotonic 1,2-propylene methy1v1nyl 1,2-propylene-. hexinnethlauryl 1 ylene. yene. 29 1,2-butylene methyl brityaaldeisobutylene..- propyl 1s0butylene.. 1,2-butylcnc methyl 1 y e. 30 ethylene octadecyl acrolein he itmethhe amethethylene octadecyl 1 yene. yene. 31 pentamethamyl l'ormaldeethylene ethylene pentamethamyl 2 ylene hyde 32 ethylene methyl do 33 do do do 6 34-- do do .do- ..d0 -do do 7 35 tetrmncthheptyl acetaldehyde trimethylene.. tnmethylenm. tetrlameth- 3 ylene. yene. 36 (lo propyl propionalethylene ethylene .do propyl a dehyde.

Example 37.A solution of 266 pts. by wt. of ethylene 2-thione) Other polymeric thiadiazinethiones of this invention Continued stirring of Example 51.The following wettable powder compoof the active ingredient. when sprayed on tomato foliage, substantially prevents infection by early blight (Alternaria solani).

sition is diluted with water to give a 0.2% concentration The resultant composition,

Percent 5,5 [(tetrahyd1'o-2-thiono-2H-1,3,5-thiadiazin-3,5-

ylene)diethylene]bis(tetrahydro 3 methyl-2H- l,3 ,5-thiadiazine-2-thione) 50 Sodium lauryl sulfate 0.5 Sodium lignin sulfonate 1.0

Kaolin clay 48.5

Example 52.The following wettable powder when of 100 gallons having the subgeneric structure 111 shown above can be prepared similarly by substituting equivalent molar quantities of the reactants listed in Table IV below for the solani) thiadiazin 3,5

dispersed in water at a concentration gallons of water and sp of 2 pounds per 100 rayed on tomato foliage at a rate per acre, prevents early blight (Alternaria Percent 3,3 ethylenebis[(tetrahydro 2 thiono-2H-1,3,5- -ylene) diethylene] bis(tetral1ydro-5- reactants of Example 37 above. Multiples of the equivfi i g g g' fg a g q alent quantities of the difunctional reactants as shown in y p a ene Omc ac! 5 mm s h 1 thi d Low viscosity methyl cellulose 0.25 Table I react to give t e p0 ymenc a lazlne- Siliaa 1 0 Table IV Reactants Products Obtained of SubgenIeric Structure III where R, R1, R1,

3Zl1'G- di-HCI salt Monodi- Alkylencblsdi- Ex. No. of dizunine Aldehyde thiocarbamic thiocarbamie R R1 R R 11 acid, N a+ acid, 2N a+ salt 38.. ethyleneformaldehyde. ethyl ethylene H eth lene eth lene th 1 39 do acetaldehyde-- propyl tetrlamethmethyl tctgtmethd gwi rnfl; i

yene. lene. 40 tetrlamethcrotonlc allyl ethylene methylvinyL. etl l ylene tetramethallyl 1 yene. lene. 41 hexamethformaldehyde methyl hexameth- H hexameth he ltamethmethyl 1 ylene. ylene. ylene. ylenc. 42 ethylene bt ty rialde lauryl ethylene propyl ethylene ethylene lnuryl. 1 43 do do vinyl do 44 tr1methyleneisobutylene.-. isopropyl is0butylene 45 ethylene eth lene eth l 46 do me do do d acetaldehyde 49 pentamethpropional- -dc pentamethylcne. dehyde. ylene. 50 ethylene formaldehyded0 ethylene Example 53.A fungicidal dust composition of 5,5- ethylenebis[(tetrahydro 2 thiono-2H-l,3,5-thiadiazin- 3,5 ylene)diethylene1bis(tctrahydro-3-methyl-2H-1,3,5- thiadiazine-Z-thione) is prepared. When dusted on bean plants at the rate of pounds of active ingredient per acre, bean rust (Uromyces appendiculatus) is controlled.

Percent 5,5 ethylenebis[(tetrahydro 2 thiono-2H-l,3,5- thiadiazin 3,5-ylene)diethylene1bis(tetrahydro-3- methyl-2H-l,3,5-thiadiazine-2-thione) 20.0

Stearated calcium carbonate 80.0

Example 54.Poly 3,3 ethylenebis[(tetrahydro-2- thiono 2H 1,3,5 -thiadiazin-3,5-ylene)diethylene1bis- (tetrahydr-o-S-methyl-ZH-l,3,5-thiadiazine-2-thione) is applied to tomato foliage as an aqueous dispersion at a concentration of 0.2%. When the spray deposit dries, the foliage is inoculated wth the spores of the early blight fungus (Alternaria solani). After a suitable incubation time the leaves are examined for disease. It is found that the treated leaves have very little infection while the untreated control leaves have 100% disease.

The same compound is applied to bean plants as an aqueous suspension at a concentration of 0.008%. When the spray deposit has dried, the plants are exposed to infection by the spores of bean rust (Uromyces appendicitlatus). After a suitable incubation period it is found that the treated plants have very little infection whereas the untreated control plants have 100% infection.

Example 55.This compound is formulated as a dust that is suitable for application by means of conventional dusting equipment by blending the active and minor diluents together and passing them through a micropulverizer, then blending the product with the major diluent in a ribbon blender.

Percent 5,5 [(tetrahydro-Z-thiono-ZH-1,3,5-thiadiazin-3,5-

ylene) diethylene] bis (tetrahydro-3-allyl 2H-1,3 ,5 thiadiaZine-2-thione) 25 .0 Pyrophyllite 69.0 6.0

Attapulgite This fungicidal dust is prepared by blending the listed ingredients and passing them through a micropulverizer. When the composition is dusted on pear trees at the rate of 10 pounds per acre of actual ingredient, it is found to prevent pear scab (Vemuria pyrina).

Example 5 7.3,3'-ethylenebis[(tetrahydro 2 thiono- 2H 1,3,5-thiadiaZin-3,5-ylene)diethylene]bis(tetrahydro- 5-ethyl-2H-l,3,5-thiadiazine-2-thione) is formulated to a wettable powder fungicidal composition by blending the list of ingredients together and passing them twice through a micropulverizer. The resulting powder disperses readily in Water to yield a fungicidal spray composition.

Percent Ex. 23 (named above) 8-0.0 Alkylnaphthalene sulfonic acid, sodium salt 0.75 Low viscosity methyl cellulose 0.25 Silica 19.0

Example 58.A wettable powder of the following composition is prepared.

Percent 5 ,5 [(tetrahydro-2-thiono-2H-l,3,5-thiadiazin-3,5- ylene)diethylene]bis(tetrahydro-3-isopropyl QH- 1,3,5 -thiadiaZine-2-thione) 80.0

Alkylnaphthalene sulfonic acid, sodium salt 0.75 Low viscosity methyl cellulose 0.25 Diatomaceous earth 19.0

This wettable powder, when dispersed in water at a concentration of 2 pounds per gallons of water and sprayed on apple trees at the rate of 100 gallons per acre prevents infection by apple scab (Venturia inaequalis).

Example 59.-

Percent Poly-(5,5'-ethylenebis[(tetrahydro 2 thiono-ZH- 1,3,5-thiadiazin 3,5 ylene)diethylene]bis(tetrahydro-3-methyl-2H-1,3,5-thiadiazine-2-thione) 30.0 Octyl alcohol 0.005 Sodium lignin sulfonate 15.0 Hydrated attapulgite 1.75 Water 53.45

S S H H C 0 Y is selected from the group consisting of and 1 1 R is selected from the group consisting of hydrogen, alkyl of 1-3 carbons, and alkenyl of 1-3 carbons; R and R are selected from the group consisting of alkylene of 26 carbons; R is selected from the group consisting of hydrogen alkyl of 1-18 carbons and alkenyl of 1-18 car- 5 bons; and n is a positive whole number.

References Cited in the file of this patent UNITED STATES PATENTS 2,838,389 Yoder June 10, 1958 10 12 Harmon et a] Aug. 18, 1959 Bluestone Jan. 12, 1960 Laubach Oct. 11, 1960 Teufel Oct. 18, 1960 FOREIGN PATENTS France Mar. 28, 1960 

